Removal of vanadium and/or sodium from petroleum hydrocarbons



nited States Patent D A:

R ovAL or VANADTUM AND/R SODIUM FR M EPETROLEUM HYQRQ A S i 2,970,957 c m scara. 7, 1,961

have lost activity .fordesulphurisation for the purposes of the present application.

The invention is applicable to the preparation of residual fuels of low sodium and vanadium content, such fuels Roy Purdy Northcott and Ronald "Lester, Sunbury-oubeing especially suitable forthe operation of gas turbines Thame's, England, assignors to The British Petroleum a d hi di l i p y l London, England, a Bl'ltlsh 1 The invention is also applicable to the removal of vanastock corpomhon dium and/or sodium from crude oils and crude oil resi- No Drawing Filed Man 21 1956, Sen 57 14 dues prior to the treatment of the hydrocarbons over a hydrofining catalyst for the removal of sulphur. The Clam p ys appllcatlon Great Blltam 24, 1955 hydrofining catalyst may advantageously consist of a 5 him Cl 2o8 251 fresh catalyst of the k nd described.

C The process according to the invention may be carried This invention relates to the removal of vanadium out Over a Wlde range of condltlons as follows: and/ or sodium from petroleum hydrocarbons, more par- Temperature F 750. 00 ticularly from crude petroleum and crude petroleum pressure p,s i ga 500-1500 residpes- Space velocity v./v./hr 0.5-5.0 It is known that sodium and vanadium may be removed G recyde rate ,f b 1,000-10 000 to a considerable extent from petroleum hydrocarbons by Th be d d h f contacting the hydrocarbons at elevated temperature and th i W1 9 6 Wlt re erence to pressure in the presence of hydrogen with a catalyst con- 0 owmg examp E l sisting of or comprising the oxides of cobalt and molybmmp denum supported on a metal oxide, preferably alumina. Feedstock Kuwait crude oil. Such catalysts are relatively expensive however, and at- Sulphur content 2.54% wt. tempts have been made to find alternative and cheaper Vanadium content 24 p.p.m. materials for eflecting removal of the sodium and vana- Sodium content 6 p.p.m. dium. These attempts have to some extent succeeded, Pressure 1,000 p.s.i.ga. bauxite having been suggested, but we have now discovered Temperature 780 F. a still cheaper material that may be used for the purpose Space velocity 1.0 v./v./hr. in question. Gas recycle rate 4,000 s.c.f./b.

No. of run 1 2 3 4 6 7 8 9 10 Total catalyst life, hr. on

stream 0-200 200400 4004500 600-800 8004.000 1, 000-1, 200 1, 200-1, 400 1, 400-1, 000 1, 000-1, 800 1,800-2, 000 Sulphur content of product, percent wei ht"... 0.45 0. 57 0. 02 0. 01 0. 74 0.80 0.90 0. 95 0.98 1.01 Sulphur removal, percent 82. 3 77. 6 75. 3 75. 7 70. 4 67. 7 64. 5 62. 2 61. O 59. 8 Vanadium content of product, p.p.m..... 3 2 5 4 4 Vanadium remova percent 88 92 70 s3 83 Sodium content of prodduct, p.p.m 1 1 Sodium removal, percent. 83 83 It is known that a catalyst of the kind consisting of or comprising the oxides of cobalt and molybdenum, as such or in combined form, incorporated with a metal oxide support, usually alumina, sufiers a permanent loss of activity for desulphurisation after repeated regeneration, but we have now found that the activity of the catalyst for sodium and vanadium removal does not decline at the same rate, and that the catalyst may be used to elfect a valuable degree of removal of these elements after its effectiveness for desulphurisation has fallen below an economic level. 1

According to the present invention therefore, a process for the removal of sodium and/or vanadium from petroleum hydrocarbons comprises contacting the hydrocarbons at elevated temperature and pressure and in the presence of hydrogen with a catalyst of the kind described which has lost activity for desulphurisation after repeated regeneration.

In order to determine whether the catalyst has lost activity for desulphurisation, the catalyst is used to hydrofine a Kuwait crude oil or crude oil residue under the following conditions:

Temperature F 780 Pressure ..p.s.i.ga 1,000 Space velocity v./v./hr.. 1.0 Hydrogen recycle rate s.c.f./b 4,000

It the residue boiling above 371 C. has a sulphur com It will be seen that while the sulphur removal declined from at the beginning of the test to 60% after 2000 hours on stream and 9 regenerations, the vanadium removal remained substantially constant at an average value of Under the same procem conditions, bauxite will give approximately 70% vanadium removal.

We claim:

1. A process for the removal of sodium and vanadium from petroleum hydrocarbons containing at least one of these substances which comprises contacting said petrm leum hydrocarbons at elevated temperature and pressure and in an atmosphere comprised of hydrogen with a spent and unregenerable desulfurization catalyst comprising the oxides of cobalt and molybdenum incorporated with a metal oxide support.

2. A process according to claim 1, which is carried out at a temperature of 750 to 800 F., a pressure of 500 to 1500 p.s.i.ga., a space velocity of 0.5 to 5.0 v./v./hr., and a gas recycle rate of 1000 to 10,000 s.c.f./lb.

3. A process for the hydrocatalytic desulfurization of petroleum hydrocarbons which contain at least one of the metal contaminants sodium or vanadium which comprises contacting said petroleum hydrocarbons at elevated temperature and pressure and in an atmosphere comprising hydrogen with a spent and unregenerable desulfurization catalyst which comprises the oxides of cobalt and molybdenum incorporated with a metal oxide support and subsequently contacting said, hydrocarbons at elevated. tem- 1000 to 10,000 s.c.f./b.

perature and pressure and in the presence of hydrogen with an active cobalt-molybdenum desulfurization catalyst 4. A process according to claim 3, in which the contact ing of said hydrocarbon with said spent and unregenerabie desulfurization catalyst is carried out'at'a temperature of 750 to 800 F., a pressure of 500 to 1500 p.s.i.ga., a space velocity of 0.5 to 5.0 v./v./hr., and a gas recycle rate of 5. ,A process according to claim 4 wherein the metal oxide support is alumina. V v,

References Cited in the file of this patent" UNITED STATES 'PATENTS Szayna Feb. 17, 1942 Szayna Dec. 21, 1943 Becker June 19, 1945 Burk et al June 4, 1946 McKinley Sept. 21, 1954 Nicholson H--. Sept. 13, 1955 Porter et al Aug. 7, 1956 Bieber et al. Aug. 5, 1958 

1. A PROCESS FOR THE REMOVAL OF SODIUM AND VANADIUM FROM PETROLEUM HYDDROCARBONS CONTAINING AT LEAST ONE OF THESE SUBSTANCES WHICH COMPRISES CONTACTING SAID PETROLEUM HYDROCARBONS AT ELEVATED TEMPERATURE AND PRESSURE AND IN AN ATMOSPHERE COMPRISED OF HYDROGEN WITH A SPENT AND UNREGENERABLE DESULFURIZATION CATALYST COMPRISING THE OXIDES OF COBALT AND MOLYBDENUM INNCORPORATED WITH A METAL OXIDE SUPPORT. 